As humans move beyond low-Earth orbit, where resupply of water will be impractical or impossible, systems that can ensure the provision of safe, clean, recycled water are critical. Current methods of microbial detection for spacecraft water are crew time- and consumable-dependent and would not be possible during periods of dormancy. One potential method for microbial detection that can be performed remotely and without sample preparation is the analysis of headspace to determine if specific volatile organic compounds (VOC) are present. Here, the use of gas chromatography-mass spectrometry (GC-MS) to analyze the headspace above cultures of bacteria returned from the International Space Station is discussed. Three species of bacteria: Ralstonia pickettii, Burkholderia contaminans, and Klebsiella aerogenes, were cultured, and the VOCs emitted by each culture were analyzed through headspace GC-MS analysis. A number of species-specific compounds were detected, but a particular marker, dimethyl disulfide, was present in all species and test conditions. The isolates' genomes were sequenced, and genes encoding for enzymes that could contribute to the production of dimethyl disulfide were identified. This analysis supported the premise that each organism examined was capable of producing this compound as a byproduct of methionine metabolism and suggests that dimethyl disulfide would be a suitable target compound for the detection of process escapes in the area of microbial control in future spacecraft water recovery systems. The results shown here suggest that the use of MS-based techniques for headspace VOC analysis is a promising avenue for the detection of these common spacecraft bacteria in spaceflight wastewater.

We report four Chitinophaga sp. strains isolated from wastewater collected onboard the International Space Station. Here, we present three finished and one draft genome. Taxonomic ranks established by genome-based analysis indicate that these Chitinophaga sp. strains represent candidates for a new species.

One of the primary concerns when designing CO2 scrubber systems that will be integrated with a Sabatier reactor to produce water and methane is the amount of water released from the scrubber. Because the gas stream entering a Sabatier reactor must be compressed, water entering the reactor can condense and compromise the integrity of the system, thus rendering its valuable conversion capability useless. When the Johnson Space Center Environmental Chemistry Laboratory was tasked to develop an assay to quantify the water concentration in air samples from CO2 scrubbers, additional testing was also performed to see if any other compounds were being concentrated on the scrubbers. It was thought that the efficiency of the scrubber systems could be quantified by comparing the differences in samples from the ambient air on the International Space Station (ISS) to the exit gas of the scrubber. As this analysis was carried out, it became evident that the concentrations of certain volatile compounds were higher in the samples from the scrubbers than they were in nominal environmental samples. This meant these compounds were being retained and concentrated on the scrubber beds. Based on this finding, concerns were raised about their potential for these compounds to poison the Sabatier reactor. Further investigation was required to identify these compounds due to their high concentrations and unique matrix of the CO2 scrubber exhaust. This paper describes these events as well as the process that was developed to identify the volatile compounds that increased. An examination of how much the certain compounds can be concentrated by the scrubber systems is also included.

The International Space Station (ISS) Air Quality Monitors (AQMs) have provided targeted in-flight analysis of volatile organic compounds (VOCs) in the ISS atmosphere since early 2013. During their initial half decade of use covering multiple sets of units, the AQMs performed well, meeting their validation criteria and showing excellent accuracy compared to archival samples. In addition to routine environmental monitoring, the AQMs have also been used during a number of contingency situations and investigations related to Environmental Control and Life Support Systems (ECLSS). These include a potential ammonia leak, increases in atmospheric ethanol, and efforts to locate potential sources of polydimethylsiloxanes that lead to the production of dimethylsilanediol (DMSD) in the US Water Processor Assembly (WPA). As the fleet of AQMs has aged, several issues have arisen. These have ranged from pervasive problems on electronics boards to loss of sensitivity due to operating in an elevated CO2 environment. The most notable issue encountered during on-orbit operations was incorrect identification of compounds. This initially occurred in mid-2020, when AQM1 reported the presence of benzene. While the AQM team questioned the validity of these results, the concentration of the "benzene" continued to increase and eventually exceeded the 30- and 180-day Spacecraft Maximum Allowable Concentration (SMAC). This led to wide-ranging efforts by a number of groups aimed at understanding the situation and identifying the source of the "benzene." AQM1 failed after being relocated to the Russian Segment as part of the investigation, and the unit was returned for evaluation. When archive samples collected while the AQM was measuring elevated benzene showed no detectable benzene, the focus of the investigation shifted to determining the cause of the false positive readings. Here, we will discuss the results of this investigation by the AQM team, potential causes of the interference, and subsequent reporting of AQM1 results.

The mechanisms of particle-induced pathogenesis in the lung remain poorly understood. Neutrophilic inflammation and oxidative stress in the lung are hallmarks of toxicity. Some investigators have postulated that oxidative stress from particle surface reactive oxygen species (psROS) on the dust produces the toxicopathology in the lungs of dust-exposed animals. This postulate was tested concurrently with the studies to elucidate the toxicity of lunar dust (LD), which is believed to contain psROS due to high-speed micrometeoroid bombardment that fractured and pulverized lunar surface regolith. Results from studies of rats intratracheally instilled (ITI) with three LDs (prepared from an Apollo-14 lunar regolith), which differed 14-fold in levels of psROS, and two toxicity reference dusts (TiO2 and quartz) indicated that psROS had no significant contribution to the dusts' toxicity in the lung. Reported here are results of further investigations by the LD toxicity study team on the toxicological role of oxidants in alveolar neutrophils that were harvested from rats in the 5-dust ITI study and from rats that were exposed to airborne LD for 4 weeks. The oxidants per neutrophils and all neutrophils increased with dose, exposure time and dust's cytotoxicity. The results suggest that alveolar neutrophils play a critical role in particle-induced injury and toxicity in the lung of dust-exposed animals. Based on these results, we propose an adverse outcome pathway (AOP) for particle-associated lung disease that centers on the crucial role of alveolar neutrophil-derived oxidant species. A critical review of the toxicology literature on particle exposure and lung disease further supports a neutrophil-centric mechanism in the pathogenesis of lung disease and may explain previously reported animal species differences in responses to poorly soluble particles. Key findings from the toxicology literature indicate that (1) after exposures to the same dust at the same amount, rats have more alveolar neutrophils than hamsters; hamsters clear more particles from their lungs, consequently contributing to fewer neutrophils and less severe lung lesions; (2) rats exposed to nano-sized TiO2 have more neutrophils and more severe lesions in their lungs than rats exposed to the same mass-concentration of micron-sized TiO2; nano-sized dust has a greater number of particles and a larger total particle-cell contact surface area than the same mass of micron-sized dust, which triggers more alveolar epithelial cells (AECs) to synthesize and release more cytokines that recruit a greater number of neutrophils leading to more severe lesions. Thus, we postulate that, during chronic dust exposure, particle-inflicted AECs persistently release cytokines, which recruit neutrophils and activate them to produce oxidants resulting in a prolonged continuous source of endogenous oxidative stress that leads to lung toxicity. This neutrophil-driven lung pathogenesis explains why dust exposure induces more severe lesions in rats than hamsters; why, on a mass-dose basis, nano-sized dusts are more toxic than the micron-sized dusts; why lung lesions progress with time; and why dose-response curves of particle toxicity exhibit a hockey stick like shape with a threshold. The neutrophil centric AOP for particle-induced lung disease has implications for risk assessment of human exposures to dust particles and environmental particulate matter.

Abstract Humans will set foot on the Moon again soon. The lunar dust (LD) is potentially reactive and could pose an inhalation hazard to lunar explorers. We elucidated LD toxicity and investigated the toxicological impact of particle surface reactivity (SR) using three LDs, quartz, and TiO2. We first isolated the respirable-size-fraction of an Apollo-14 regolith and ground two coarser samples to produce fine LDs with increased SR. SR measurements of these five respirable-sized dusts, determined by their in-vitro ability to generate hydroxyl radicals (•OH), showed that ground LDs > unground LD ≥ TiO2 ≥ quartz. Rats were each intratracheally instilled with 0, 1, 2.5, or 7.5 mg of a test dust. Toxicity biomarkers and histopathology were assessed up to 13 weeks after the bolus instillation. All dusts caused dose-dependent-increases in pulmonary lesions and toxicity biomarkers. The three LDs, which possessed mineral compositions/properties similar to Arizona volcanic ash, were moderately toxic. Despite a 14-fold •OH difference among these three LDs, their toxicities were indistinguishable. Quartz produced the lowest •OH amount but showed the greatest toxicity. Our results showed no correlation between the toxicity of mineral dusts and their ability to generate free radicals. We also showed that the amounts of oxidants per neutrophil increased with doses, time and the cytotoxicity of the dusts in the lung, which supports our postulation that dust-elicited neutrophilia is the major persistent source of oxidative stress. These results and the discussion of the crucial roles of the short-lived, continuously replenished neutrophils in dust-induced pathogenesis are presented.

The binding of SO2 on gas-phase gold cluster anions, Au-N(-), and their hydroxide counterparts, AuNOH-, have been studied using density functional theory combined with flow reactor/time-of-flight mass spectrometry techniques. SO2 is adsorbed on all of the Au-N(-) and AuNOH- clusters (N = 1-8) and the hydroxide clusters are more active than the bare anionic clusters. Successive additions of SO2 molecules (up to four) have been analyzed. In all cases, anionic clusters are shown to bind multiple SO2 molecules. Theoretical analyses are in agreement with the experimental results, showing that the addition of more than one molecule is thermodynamically favorable. Larger clusters do not necessarily absorb more molecules, as different SO2 binding motifs on these clusters are present. These results provide important insight for the potential use of these anionic clusters as SO2 hunters.

Maintaining a safe supply of potable water is of utmost importance when preparing for long-duration spaceflight missions, with the minimization of microbial growth being one major aspect. While biocides, such as ionic silver, historically have been used for microbial control in spaceflight, their effectiveness is sometimes limited due to surface reactions with the materials of the storage containers that reduce their concentrations below the effective range. For the Multi-Purpose Crew Vehicle, the primary wetted materials of the water storage system are stainless steel and a titanium alloy, and ionic silver has been chosen to serve as the biocide. As an attempt to understand what processes might reduce the known losses of silver, different treatment processes were attempted and samples of the wetted materials were tested, individually and together, to determine the relative loss of biocide under representative surface area-to-volume ratios. The results of testing presented here showed that the materials could be treated by a nitric acid rinse or a high-concentration silver spike to reduce the loss of silver and bacterial growth. It was also found that the minimum biocidal concentration could be maintained for over 28 days. These results have pointed to approaches that could be used to successfully maintain silver in spacecraft water systems for long-duration missions.

For the past 4 years, the Air Quality Monitor (AQM) has been the operational instrument for measuring trace volatile organic compounds on the International Space Station (ISS). The key components of the AQM are the inlet preconcentrator, the gas chromatograph (GC), and the differential mobility spectrometer. Onboard the ISS are two AQMs with different GC columns that detect and quantify 22 compounds. The AQM data contributes valuable information to the assessment of air quality aboard ISS for each crew increment. The US Navy is looking to update its submarine air monitoring suite of instruments and the success of the AQM on ISS has led to a jointly planned submarine sea trial of a NASA AQM. In addition to the AQM, the Navy is also interested in the Multi-Gas Monitor (MGM), which measures major constituent gases (oxygen, carbon dioxide, water vapor, and ammonia). A separate paper will present the MGM sea trial preparation and the analysis of most recent ISS data. A prototype AQM, which is virtually identical to the operational AQM, has been readied for the sea trial. Only 1 AQM will be deployed during the sea trial, but this is sufficient for NASA purposes and to detect the compounds of interest to the US Navy for this trial. The data from the sea trial will be compared to data from archival samples collected before, during, and after the trial period. This paper will start with a brief history of past collaborations between NASA and the U.S. and U.K. navies for trials of air monitoring equipment. An overview of the AQM technology and protocols for the submarine trial will be presented. The majority of the presentation will focus on the AQM preparation and a summary of available data from the trial.

Spacecraft are partially- or fully-closed environments that demand environmental monitoring to protect the health of the crew and the vehicle. This article will detail the history of air and water monitoring on U.S. spacecraft from early in the human spaceflight era and will use the lessons learned to project the needs for commercial crew vehicles and exploration missions. Many sources of air and water pollutants exist on spacecraft (e.g., humans, material off-gas products, system chemicals, and experiments), which are scrubbed by various Environmental Control and Life Support Systems (ECLSS). Environmental monitoring is important because the rate of removal seldom, if ever, equals or exceeds the rate of generation. As an example, carbon dioxide levels are “controlled” in spacecraft, but the levels are never close to zero. Much of the recycled water comes from spacecraft air condensate; therefore, contaminants in the air can also have a dramatic effect on potable water reclamation/purification and resulting water quality. In addition, potential system leaks and spills can contaminate the air and/or water. The experiences of humans working in closed environments (spacecraft and submarines) show that engineering controls are not sufficient to completely protect the crew from environmental hazards. This article will highlight the fact that characteristics of environmental monitors go beyond being lower power and small instruments. How much monitoring is required and the characteristics of the monitors all depend on the mission scenario, particularly mission durations and the ability of the crews to return to Earth or seek safe haven in the event of environmental contamination of their primary vehicle.

When preparing for long-duration spaceflight missions, maintaining a safe supply of potable water is of the utmost importance. One major aspect of that is ensuring that microbial growth is minimized. Historically, this challenge has been addressed through the use of biocides. When using biocides, the choice of materials for the storage containers is important, because surface reactions can reduce biocide concentrations below their effective range. In the water storage system baselined for the Orion vehicle, the primary wetted materials are stainless steel (316 L) and a titanium alloy (Ti6Al4V). Previous testing with these materials has shown that the biocide selected for use in the system (ionic silver) will plate out rapidly upon initial wetting of the system. One potential approach for maintaining an adequate biocide concentration is to spike the water supply with high levels of biocide in an attempt to passivate the surface. To evaluate this hypothesis, samples of the wetted materials were tested individually and together to determine the relative loss of biocide under representative surface area-to-volume ratios after 24 hours. Additionally, we have analyzed the efficacy of disinfecting a system containing these materials by measuring reductions in bacterial counts in the same test conditions. Preliminary results indicate that the use of titanium, either individually or in combination with stainless steel, can result in over 95% loss of biocide, while less than 5% is lost when using stainless steel. In bacterial testing, viable organisms were recovered from samples exposed to the titanium coupons after 24 hours. By comparison, no organisms were recovered from the test vessels containing only stainless steel. These results indicate that titanium, while possessing some favorable attributes, may pose additional challenges when used in water storage tanks with ionic silver biocide.

Low molecular weight polar organics are commonly observed in spacecraft environments. Increasing concentrations of one or more of these contaminants can negatively impact Environmental Control and Life Support (ECLS) systems and/or the health of crew members, posing potential risks to the success of manned space missions. Ambient plasma ionization mass spectrometry (MS) is finding effective use as part of the analytical methodologies being tested for next-generation space module environmental analysis. However, ambient ionization methods employing atmospheric plasmas typically require relatively high operation voltages and power, thus limiting their applicability in combination with fieldable mass spectrometers. In this work, we investigate the use of a low power microplasma device in the microhollow cathode discharge (MHCD) configuration for the analysis of polar organics encountered in space missions. A metal-insulator-metal (MIM) structure with molybdenum foil disc electrodes and a mica insulator was used to form a 300 μm diameter plasma discharge cavity. We demonstrate the application of these MIM microplasmas as part of a versatile miniature ion source for the analysis of typical volatile contaminants found in the International Space Station (ISS) environment, highlighting their advantages as low cost and simple analytical devices.

The water produced by the U.S. Water Processor Assembly (WPA) on the International Space Station had virtually undetectable levels of total organic carbon (TOC) during the first 18 months of operation. In 2010, the TOC in the WPA product water rose to approx. 2 mg/L. The maximum allowable TOC concentration in the product water is 3.0 mg/L. Ground analysis indicated that > 90% of this increase was due to dimethylsilanediol (DMSD). Since then, recurring increases in TOC attributed to DMSD have occurred every 12-18 months. In 2015, a new compound was determined to be responsible for the TOC increase. This new contaminant was identified as monomethylsilanetriol (MMST). This poster details the efforts to identify and quantify DMSD and MMST. DMSD was initially discovered as a stray peak in a routine GC/MS analysis used to measure glycols. This method was not suitable for routine analysis of DMSD because of extreme carryover problems. MMST was discovered and identified using direct infusion electrospray ionization (ESI) mass spectrometry. The identification was confirmed by purchasing an MMST standard and analyzing it by HPLC with refractive index (RI) detection. An LC/MS method has been developed, based on the LC/RI method that quantifies both DMSD and MMST in a 14-minute isocratic run. This method employs atmospheric pressure chemical ionization (APCI) and a single quadrupole mass spectrometer operated in negative mode with selected ion monitoring.

We separated the respirable dust and other size fractions from Apollo 14 bulk sample 14003,96 in a dry nitrogen environment. While our toxicology team performed in vivo and in vitro experiments with the respirable fraction, we studied the size distribution and shape, chemistry, mineralogy, spectroscopy, iron content and magnetic resonance of various size fractions. These represent the finest-grained lunar samples ever measured for either FMR np-Fe-0 index or precise bulk chemistry, and are the first instance we know of in which SEM/TEM samples have been obtained without using liquids.The concentration of single-domain, nanophase metallic iron (np-Fe-0) increases as particle size diminishes to 2 mu m, confirming previous extrapolations. Size-distribution studies disclosed that the most frequent particle size was in the 0.1-0.2 mu m range suggesting a relatively high surface area and therefore higher potential toxicity.Lunar dust particles are insoluble in isopropanol but slightly soluble in distilled water (similar to 0.2 wt%/3 days). The interaction between water and lunar fines, which results in both agglomeration and partial dissolution, is observable on a macro scale over time periods of less than an hour.Most of the respirable grains were smooth amorphous glass. This suggests less toxicity than if the grains were irregular, porous, or jagged, and may account for the fact that lunar dust is less toxic than ground quartz. (C) 2014 IAA. Published by Elsevier Ltd. All rights reserved.

ABSTRACT The National Aeronautics and Space Administration (NASA) has plans to further their manned space exploration to Mars and possibly beyond. The potential toxicity of lunar and Martian dusts to astronauts is a big concern. Primary routes of exposure for astronauts are dermal contact, ocular contact, and inhalation. In this study, we focused on dermal contact exposure using human skin cells to investigate the cytotoxic and genotoxic effects of two fractions of lunar dust simulant (JSC-1A-vf, JSC-1A-f) and a Mars dust simulant (Mars-1A), and compared them to urban dust (urban particulate matter), as urban dust toxicity is better understood and thus, provides a good comparison. Our data show the three simulants and urban dust are cytotoxic to human skin cells. The JSC-1A-vf lunar dust simulant is more cytotoxic than the JSC-1A-f and urban dust. Urban dust cytotoxicity is similar to Mars dust simulant after 120 h exposure. All three dust simulants and urban dust show similar low genotoxicity effects. Our data suggest extraterrestrial dust can damage skin cells and may have the potential to be harmful to humans.

In the history of manned spaceflight, environmental monitoring has relied heavily on archival sampling. However, with the construction of the International Space Station (ISS) and the subsequent extension in mission duration up to one year, an enhanced, real-time method for environmental monitoring is necessary. The station air is currently monitored for trace volatile organic compounds (VOCs) using gas chromatography-differential mobility spectrometry (GC-DMS) via the Air Quality Monitor (AQM), while water is analyzed to measure total organic carbon and biocide concentrations using the Total Organic Carbon Analyzer (TOCA) and the Colorimetric Water Quality Monitoring Kit (CWQMK), respectively. As mission scenarios extend beyond low Earth orbit, a convergence in analytical instrumentation to analyze both air and water samples is highly desirable. Since the AQM currently provides quantitative, compound-specific information for air samples and many of the targets in air are also common to water, this platform is a logical starting point for developing a multimatrix monitor. Here, we report on the interfacing of an electrothermal vaporization (ETV) sample introduction unit with a ground-based AQM for monitoring target analytes in water. The results show that each of the compounds tested from water have similar GC-DMS parameters as the compounds tested in air. Moreover, the ETV enabled AQM detection of dimethlsilanediol (DMSD), a compound whose analysis had proven challenging using other sample introduction methods. Analysis of authentic ISS water samples using the ETV-AQM showed that DMSD could be successfully quantified, while the concentrations obtained for the other compounds also agreed well with laboratory results.

The air quality monitor (AQM) began operations on the International Space Station (ISS) in March 2013 and was validated for operational use in January 2014. The AQM is a gas chromatograph-differential mobility spectrometer that currently monitors 22 target compounds in the ISS atmosphere. Data are collected twice per week, although data collection can be more frequent in contingency situations. In its second year, the AQM has provided data to decision-makers on several ISS contaminant related issues in both air and water. AQM has been used in strictly air incidents, such as a potential ammonia leak, and to investigate air contaminants affecting the water processing (excess ethanol). In the latter case data from water monitors and AQM were compared to understand the issue with the water processor. Additionally, the AQM has been moved to different ISS modules to determine whether air is sufficiently mixed between modules so that a central LAB module location is representative of the entire ISS atmosphere. Historic data on the ISS atmosphere in different modules from archival samples (ground lab analysis) suggest that the atmosphere is usually homogenous. This presentation will briefly describe the technical aspects of the AQM operations and summarize the validation results. The main focus of the presentation will be to discuss the results from the AQM survey of the ISS modules and to show how the AQM data has contributed to an understanding of environmental issues that have arisen on ISS. Presentation of a potential ammonia leak (indicated by an alarm) in 2015 will illustrate the use and value of the AQM in such situations.